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Process for the Production of Chlorinated Propanes Verfahren Zur Herstellung Von Chlorierten Propanen Procédé De Production De Propanes Chlorés

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Process for the Production of Chlorinated Propanes Verfahren Zur Herstellung Von Chlorierten Propanen Procédé De Production De Propanes Chlorés (19) TZZ __T (11) EP 2 785 671 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 17/10 (2006.01) C07C 19/01 (2006.01) 01.03.2017 Bulletin 2017/09 (86) International application number: (21) Application number: 12799450.7 PCT/US2012/067268 (22) Date of filing: 30.11.2012 (87) International publication number: WO 2013/082410 (06.06.2013 Gazette 2013/23) (54) PROCESS FOR THE PRODUCTION OF CHLORINATED PROPANES VERFAHREN ZUR HERSTELLUNG VON CHLORIERTEN PROPANEN PROCÉDÉ DE PRODUCTION DE PROPANES CHLORÉS (84) Designated Contracting States: (74) Representative: Bumke, Jakob Wenzel et al AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Greaves Brewster LLP GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Copa House PL PT RO RS SE SI SK SM TR Station Road Cheddar BS27 3AH (GB) (30) Priority: 02.12.2011 US 201161566213 P (56) References cited: (43) Date of publication of application: EP-A1- 0 164 798 WO-A1-01/38271 08.10.2014 Bulletin 2014/41 WO-A1-2009/015304 WO-A1-2009/085862 WO-A1-2012/166393 US-A- 6 118 018 (73) Proprietor: Blue Cube IP LLC US-A1- 2009 270 568 US-B1- 6 825 383 Midland MI 48674 (US) • LEWIS F. HATCH ET AL: JOURNAL OF THE (72) Inventors: AMERICAN CHEMICAL SOCIETY, vol. 74, no. 13, • GRANDBOIS, Matthew Lee 5 July 1952 (1952-07-05), pages 3328-3330, Midland, Michigan 48640 (US) XP55050199, ISSN: 0002-7863, DOI: • CHEN, Xiaoyun 10.1021/ja01133a033 Midland, Michigan 48642 (US) • KRUPER, William J. Jr. Sanford, Michigan 48657 (US) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 785 671 B1 Printed by Jouve, 75001 PARIS (FR) 1 EP 2 785 671 B1 2 Description 1,1,1,3-tetrachloropropane and chlorine, for the manu- facture of 1,1,2,3-tetrachloropropene from 1,1,1,2,3- [0001] The present invention relates to processes for pentachloropropane, for the manufacture of 1,1,2,3-tet- the production of chlorinated propanes in a nonaqueous rachloropropene from 1,1,1,3-tetrachloropropane and media. 5 chlorine, and for the manufacture of 1,1,2,3-tetrachloro- propene from carbon tetrachloride, ethylene, and chlo- BACKGROUND rine. [0008] US 6825383 B1 describes a process for re- [0002] Hydrofluorocarbon (HFC) products are widely giospecific chlorination of an aromatic or aliphatic com- utilized in many applications, including refrigeration, air 10 pound with a chlorine source comprising a metal chloride conditioning, foam expansion, and as propellants for aer- other than Cl2 or SO2Cl2 in presence of hypervalent io- osol products including medical aerosol devices. Al- dine catalyst and in acidic medium. though HFC’s have proven to be more climate friendly than the chlorofluorocarbon and hydrochlorofluorocar- BRIEF DESCRIPTION bon products that they replaced, it has now been discov- 15 ered that they exhibit an appreciable global warming po- [0009] The present invention provides efficient proc- tential (GWP). esses for the production of highly chlorinated propanes. [0003] The search for more acceptable alternatives to More particularly, the processes make use of one or more current fluorocarbon products has led to the emergence inorganic iodine salts as part of a mixed catalyst system of hydrofluoro-olefin (HFO) products. Relative to their 20 further comprising at least one Lewis acid selected from predecessors, HFOs are expected to exert less impact the group consisting of ferric chloride, antimony pentaflu- on the atmosphere in the form of a lesser, or no, detri- oride, boron trichloride, aluminum trichloride, stannic mental impact on the ozone layer and their lower GWP chloride or combinations of these. The use of inorganic as compared to HFC’s. Advantageously, HFO’s also ex- iodine salts is advantageous as compared to convention- hibit low flammability and low toxicity. 25 al processes, in that inorganic iodine salts are not as [0004] As the environmental, and thus, economic im- corrosive or volatile as elemental iodine when employed portance of HFO’s has developed, so has the demand at conventional levels, and so, are more readily and con- for precursors utilized in their production. Many desirable veniently incorporated into large scale manufacturing HFO compounds, e.g., such as 2,3,3,3-tetrafluoroprop- process. Because the present processes are conducted 1-ene or 1,3,3,3- tetrafluoroprop-1-ene, may typically be 30 in a nonaqueous media, the inorganic iodine salts are produced utilizing feedstocks of chlorocarbons, and in recoverable and/or reusable, providing significant cost particular, highly chlorinated alkanes, e.g., tetra- and savings to the process. Further cost savings are provided pentachloroalkanes. in that low intensity process conditions, e.g., low temper- [0005] Unfortunately, these higher chlorides have atures, ambient pressure and minimal reactor residence proven difficult to manufacture using acceptable process 35 time, are utilized. conditions and in commercially acceptable regioselectiv- [0010] In one aspect, the present invention provides a ities and yields. For example, conventional processes for process for the production of chlorinated propanes. The the production of pentachloropropanes provide unac- process comprises catalyzing the chlorination of a feed- ceptable selectivity to the desired pentachloropropane stream comprising one or more propanes in a nonaque- isomer(s), i.e., 1,1,2,2,3-pentachloropropane, make use 40 ous media with a mixed catalyst system comprising one of suboptimal chlorinating agents, require the use of high or more inorganic iodine salts, optionally less than 10,000 intensity process conditions and/or catalyst systems that ppm elemental iodine, and at least one Lewis acid se- are difficult to utilize in large scale production processes lected from the group consisting of ferric chloride, anti- and/or are wholly or partly unrecoverable or otherwise mony pentafluoride, boron trichloride, aluminum trichlo- unreusable. 45 ride, stannic chloride or combinations of these. Although [0006] It would thus be desirable to provide improved an inorganic iodine salt is used as part of the catalyst processes for the production of chlorocarbon precursors system, and in some advantageous embodiments, no useful as feedstocks in the synthesis of refrigerants and iodine is added to the starting propane. In some embod- other commercial products. More particularly, such proc- iments, the one or more inorganic iodine salts may com- esses would provide an improvement over the current 50 prise hypoiodites (IO-), iodites (IO2-), iodates (IO3-), state of the art if they provided a higher regioselectivity and/or periodates (IO4-), including metaperiodates and relative to conventional methods, made use of optimal orthoperiodates, or combinations of these. In some em- chlorinating agents, required low intensity process con- bodiments, the concentration of elemental iodine used, ditions, made use of catalyst systems and/or initiators if any, may be from 1 ppm to 5000 ppm, or from 5 ppm more amenable to use in large-scale processes, such as 55 to 1000 ppm, or from 10 ppm to 100 ppm. The source of those that may be recovered or otherwise reused. chlorine atoms may comprise chlorine gas, sulfuryl chlo- [0007] WO 2009/085862 A1 describes methods for the ride or a combination of these, and in some embodiments manufacture of 1,1,1,2,3-pentachloropropane from comprises sulfuryl chloride, which may also act as a dilu- 2 3 EP 2 785 671 B1 4 ent or solvent as well as a chlorine source. The propane stream comprising one or more propanes with one or may initially be unchlorinated, or, may already comprise more inorganic iodine salt and at least one Lewis acid. chlorine atoms, and may comprise any number of carbon Further, the processes take place in a nonaqueous me- atoms. dia, and as a result, the one or more inorganic iodine 5 salts may be recovered in whole or in part, and/or reused. DETAILED DESCRIPTION The use of an inorganic iodine salt is further advanta- geous in that inorganic iodine salts do not present the [0011] The present specification provides certain def- volatility and corrosion issues that can be presented by initions and methods to better define the present inven- elemental iodine when used at conventional levels, as is tion and to guide those of ordinary skill in the art in the 10 used in conventional processes for the production of practice of the present invention. Provision, or lack of the chlorinated alkanes. provision, of a definition for a particular term or phrase [0017] Any inorganic iodine salt can be used in the is not meant to imply any particular importance, or lack mixed catalyst system, and those of ordinary skill in the thereof. Rather, and unless otherwise noted, terms are art are expected to be familiar with many. Suitable ex- to be understood according to conventional usage by 15 amples include, but are not limited to, hypoiodites (IO -), those of ordinary skill in the relevant art. iodites (IO2-), iodates (IO3-), and/or periodates (IO 4-), in- [0012] The terms "first", "second", as used herein do cluding mesoperiodates and orthoperiodates, or combi- not denote any order, quantity, or importance, but rather nations of these. Specific examples of inorganic iodine are used to distinguish one element from another. Also, salts include, but are not limited to sodium iodate, silver the terms "a" and "an" do not denote a limitation of quan- 20 iodate, calcium iodate, potassium iodate, iodic acid, so- tity, but rather denote the presence of at least one of the dium periodate, potassium periodate, barium periodate, referenced item, and the terms "front", "back", "bottom", and periodic acid, and derivatives or combinations of any and/or "top", unless otherwise noted, are merely used for number of these.
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